KR102153086B1 - Novel polymer and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel polymer and an organic light emitting device including the same.

Description

Novel polymer and organic light emitting device comprising the same

The present invention relates to a novel polymer and an organic light emitting device comprising the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

On the other hand, in recent years, in order to reduce process cost, an organic light emitting device using a solution process, in particular an inkjet process, instead of a conventional deposition process has been developed. In the early days, an attempt was made to develop an organic light-emitting device by coating all organic light-emitting device layers by a solution process, but the current technology has limitations, so only HIL, HTL, and EML are processed in a solution process in the form of a regular structure, and the later process is the existing deposition process. A hybrid process that utilizes is being studied.

Accordingly, in the present invention, a material for a novel organic light-emitting device that can be used for an organic light-emitting device and can be deposited by a solution process is provided.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel polymer and an organic light emitting device comprising the same.

The present invention is a polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3):

[Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently hydrogen or C _1-10 alkyl,

L ₁ is substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,

L ₂ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,

Ar ₁ is substituted or unsubstituted C _6-60 aryl, or C _2-60 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₂ and Ar ₃ are each independently selected from the group consisting of substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O and S C _2-60 heteroaryl including any one or more,

[Formula 2]

In Chemical Formula 2,

R ₄ to R ₆ are each independently hydrogen or C _1-10 alkyl,

L ₃ is a single bond; Substituted or unsubstituted C _6-60 arylene; (Substituted or unsubstituted C _6-60 arylene)-O-; (Substituted or unsubstituted C _6-60 arylene)-O-(substituted or unsubstituted C _1-60 alkylene); Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,

[Formula 3]

In Chemical Formula 3,

R ₇ to R ₉ are each independently hydrogen or C _1-10 alkyl,

L ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,

Ar ₄ is substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O and S containing any one or more selected from the group consisting of C _2-60 heteroaryl,

Ar ₅ is hydrogen or substituted or unsubstituted C _6-60 aryl,

n is an integer from 0 to 5.

In addition, the present invention is a positive electrode; A cathode provided to face the anode; A light-emitting layer provided between the anode and the cathode; And a hole transport layer provided between the anode and the light emitting layer, wherein the hole transport layer includes the polymer.

The polymer according to the present invention may be used as a material for a hole transport layer of an organic light-emitting device, may be deposited by a solution process, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light-emitting layer 4, and a cathode 5.
2 is composed of a substrate (1), an anode (2), a hole injection layer (6), a hole transport layer (3), a light emitting layer (4), an electron transport layer (7), an electron injection layer (8) and a cathode (5). An example of an organic light emitting device is shown.

Hereinafter, it will be described in more detail to aid the understanding of the present invention.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

Etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiiadia There may be a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that two substituents are bonded to each other.

The present invention provides a polymer comprising a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3.

In the conventional solution deposition material, even if there is solubility in a solvent, the material is dissolved in a solvent used for the next layer deposition, and the layer is mixed, thereby deteriorating device performance.

However, as will be described in detail below, the polymer according to the present invention has excellent hole transport properties by the repeating unit represented by Chemical Formula 1, and the solvent orthogonality by curing the repeating unit represented by Chemical Formula 2 after deposition. It is possible to suppress interlayer mixing, and to improve the solubility and lower the curing temperature in the solution process by the repeating unit represented by Formula 3 above. Hereinafter, each repeating unit will be described.

(First repeating unit)

In the present specification, the'first repeating unit' is a repeating unit represented by Formula 1 included in the polymer according to the present invention, and has excellent hole transport properties.

Preferably, R ₁ to R ₃ are each independently hydrogen or methyl, more preferably all hydrogen.

Preferably, L ₁ is substituted or unsubstituted C _6-12 arylene, more preferably phenylene, or biphenylylene, most preferably 1,4-phenylene, or 4,4'- It is biphenylylene.

이다. Preferably, L ₂ is a single bond, substituted or unsubstituted C _6-18 arylene, more preferably phenylene, biphenylylene, or terphenylylene, most preferably 1,4-phenylene. , 1,1'-biphenylylene, or

to be.

Preferably, Ar ₁ is phenyl, biphenylyl, dimethylfluorenyl, or diphenylfluorenyl, and Ar ₁ is unsubstituted or substituted with C _1-4 alkyl or C _1-4 alkoxy. . More preferably, Ar ₁ is phenyl, biphenylyl, dimethylfluorenyl, or diphenylfluorenyl, and Ar ₁ is unsubstituted, or methyl, ethyl, propyl, isopropyl, butyl, isobutyl, It is substituted with tertbutyl, methoxy, ethoxy, propoxy, butoxy, isobutoxy, or neobutoxy.

Preferably, Ar ₂ and Ar ₃ are each independently C _6-25 aryl, more preferably each independently is phenyl, biphenylyl, dimethylfluorenyl, or diphenylfluorenyl.

Preferably, Formula 1 is any one selected from the group consisting of repeating units represented by:

On the other hand, the compound represented by Formula 1 is derived from a monomer represented by Formula 1-1:

[Formula 1-1]

In Formula 1-1, R ₁ to R ₃ , L ₁ , L ₂ and Ar ₁ to Ar ₃ are as defined in Formula 1 above.

The compound represented by Formula 1-1 can be prepared by the same method as in Scheme 1 below.

[Scheme 1]

In Reaction Scheme 1, the definitions other than X ₁ are as defined above, and X ₁ is halogen, preferably bromo or chloro. Reaction Scheme 1 is an amine substitution reaction, in which a palladium catalyst and a base are reacted to prepare the compound represented by Formula 1-1. The manufacturing method may be more specific in the manufacturing examples to be described later.

(The second repeating unit)

In the present specification, the'second repeating unit' is a repeating unit represented by Formula 2 included in the polymer according to the present invention, and includes benzocyclobutane, which is a curable reactive group. After depositing the polymer according to the present invention, through a cycloaddition reaction of the benzocyclobutane and an alkene of a third repeating unit to be described later in a thermal process, the deposited polymer has solvent resistance, and is applied to an organic light-emitting device as a solution process. can do.

Preferably, the formula 2 is represented by the following formula 2'.

[Formula 2']

Preferably, R ₄ to R ₆ are each independently hydrogen or methyl, more preferably all hydrogen.

Preferably, L ₃ is a single bond, substituted or unsubstituted C _6-12 arylene, (substituted or unsubstituted C _6-12 arylene)-O-; (Substituted or unsubstituted C _6-12 arylene)-O-(substituted or unsubstituted C _1-10 alkylene), more preferably a single bond, phenylene, -(phenylene)-O-, -(Phenylene)-O-(butane-1,4-diyl), or biphenylylene, most preferably 1,4-phenylene, or 4,4'-biphenylylene.

Preferably, Formula 2 is any one selected from the group consisting of repeating units represented by:

Meanwhile, the compound represented by Formula 2 is derived from a monomer represented by Formula 2-1:

[Formula 2-1]

In Formula 2-1, R ₄ to R ₆ , and L ₃ are as defined in Formula 2.

The compound represented by Formula 2-1 can be prepared by the same method as in Scheme 2 below.

[Scheme 2]

In Reaction Scheme 2, the definitions other than X ₂ are as defined above, and X ₂ is halogen, preferably bromo or chloro. Reaction Scheme 2 is a Suzuki coupling reaction, in which a palladium catalyst is reacted in the presence of a base to prepare a compound represented by Formula 2-1. The manufacturing method may be more specific in the manufacturing examples to be described later.

(3rd repeating unit)

In the present specification, the'third repeating unit' is a repeating unit represented by Chemical Formula 3 included in the polymer according to the present invention, and improves the solubility of the polymer according to the present invention, or because it contains a vinyl group, the curing temperature can be lowered. .

Preferably, R ₇ to R ₉ are each independently hydrogen or methyl, more preferably all hydrogen.

Preferably, L ₄ is a single bond, substituted or unsubstituted C _6-12 arylene, more preferably a single bond, phenylene, or biphenylylene, most preferably a single bond, 1,4- Phenylene, or 4,4'-biphenylylene.

Preferably, Ar ₄ is C _3-10 cycloalkyl, or C _6-12 aryl, more preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, one or two C _{1- 4} alkyl substituted phenyl, or biphenylyl.

Preferably, Ar ₅ is hydrogen, phenyl, biphenylyl, terphenylyl, or quarterphenylyl.

Preferably, Formula 3 is any one selected from the group consisting of repeating units represented by:

In the above, TMS means trimethylsilyl, and t-Bu means tert-butyl.

Meanwhile, the compound represented by Formula 3 is derived from a monomer represented by Formula 3-1:

[Formula 3-1]

In Formula 3-1, R ₇ to R ₉ , L ₄ , Ar ₄ , Ar ₅ , and n are as defined in Formula 3.

The compound represented by Chemical Formula 3-1 can be prepared by a manufacturing method as shown in Scheme 3 below.

[Scheme 3]

In Reaction Scheme 3, the definitions other than X ₃ are as defined above, and X ₃ is halogen, preferably bromo or chloro. Reaction Scheme 3 is a Suzuki coupling reaction, in which a palladium catalyst is reacted in the presence of a base to prepare a compound represented by Chemical Formula 3-1. The manufacturing method may be more specific in the manufacturing examples to be described later.

(Polymer)

The polymer according to the present invention can be prepared by polymerizing a monomer represented by Formula 1-1, a monomer represented by Formula 2-1, and a monomer represented by Formula 3-1. Preferably, the polymer according to the present invention is a random copolymer comprising the repeating unit.

In the polymer according to the present invention, x, y and z are the molar ratios of the repeating unit of Formula 1, the repeating unit of Formula 2, and the repeating unit of Formula 3 in the polymer, and x:y:z is 0.5~0.9:0.05~ 0.45: 0.05 to 0.45. The molar ratio of the polymer may be adjusted by adjusting the reaction molar ratio of the monomer represented by Formula 1-1, the monomer represented by Formula 2-1, and the monomer represented by Formula 3-1.

Preferably, the weight average molecular weight of the polymer is 15,000 to 1,000,000, more preferably 40,000 to 100,000.

Meanwhile, the polymer may be used together with a doping material. The doping material may be a compound of Formula K, an ionic compound of Formula L or Formula M, but is not limited thereto.

[Formula K]

[Formula L]

[Formula M]

(Coating composition)

The polymer according to the present invention can form an organic material layer, particularly a hole transport layer, of an organic light emitting device by a solution process. To this end, the present invention provides a coating composition comprising the polymer and a solvent according to the present invention described above.

The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the polymer according to the present invention, and examples include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o -Chlorine solvents such as dichlorobenzene; Ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Alcohol and its derivatives; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide solvents such as dimethyl sulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; Benzoate solvents such as butyl benzoate and methyl-2-methoxybenzoate; Tetralin; Solvents, such as 3-phenoxy-toluene, are mentioned. In addition, the above-described solvent may be used alone or in combination of two or more solvents.

In addition, the viscosity of the coating composition is preferably 1 cP to 10 cP, and coating is easy within the above range. In addition, the concentration of the polymer according to the present invention in the coating composition is preferably 0.1 wt / v% to 20 wt / v%.

In addition, the coating composition may further include one or two or more additives selected from the group consisting of a thermal polymerization initiator and a photopolymerization initiator.

As the thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide Peroxides such as oxide, bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, or azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile. There is an azo system, but it is not limited thereto.

As the photoinitiator, diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4-(2-hydroxyethoxy ) Phenyl-(2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1- Phenyl propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) Acetophenone-based or ketal-based photopolymerization initiators such as oxime; Benzoin ether photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Benzophenone photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, and 4-benzoylphenyl ether; Thioxanthone photoinitiators such as 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichloro thioxanthone; And ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, Other photoinitiators such as bis(2,4-dimethoxy benzoyl)-2,4,4-trimethyl pentylphosphine oxide, but are not limited thereto.

Moreover, what has a photopolymerization accelerating effect may be used alone or in combination with the photopolymerization initiator. For example, triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl benzoic acid (2-dimethylamino), 4,4'-dimethylaminobenzophenone, etc. Not limited.

In addition, the present invention provides a method of forming a hole transport layer using the above-described coating composition. Specifically, on the anode or on the hole injection layer formed on the anode, the step of coating the above-described coating composition according to the present invention by a solution process; And heat-treating or light-treating the coated coating composition.

The solution process uses the coating composition according to the present invention described above, and means spin coating, dip coating, doctor blading, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In the heat treatment step, the heat treatment temperature is preferably 150 to 230°C. In addition, the heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen. In addition, it may further include evaporating a solvent between the coating step and the heat treatment or light treatment step.

(Organic light emitting device)

In addition, the present invention provides an organic light-emitting device including the polymer according to the present invention described above. Specifically, the present invention is a positive electrode; A cathode provided to face the anode; A light-emitting layer provided between the anode and the cathode; And a hole transport layer provided between the anode and the light emitting layer, wherein the hole transport layer comprises a polymer according to the present invention.

The structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light-emitting layer 4, and a cathode 5. 2 is composed of a substrate (1), an anode (2), a hole injection layer (6), a hole transport layer (3), a light emitting layer (4), an electron transport layer (7), an electron injection layer (8) and a cathode (5). An example of an organic light emitting device is shown.

The organic light-emitting device according to the present invention can be manufactured by materials and methods known in the art, except that the hole transport layer includes the polymer according to the present invention and is manufactured as described above.

For example, the organic light-emitting device according to the present invention may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon.

In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, etc., but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

In addition, the polymer according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The manufacturing of the polymer and the organic light emitting device including the polymer according to the present invention will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Manufacture of intermediates]

Preparation of intermediates 5 and 6

After dissolving compound 1 (9 g, 27.9 mmol) and compound 2 (4.18 g, 27.9 mmol) in anhydrous THF (100 mL), Pd(PPh ₃ ) ₄ (0.32 g, 0.28 mmol) and 2M potassium carbonate (K ₂₎ CO ₃ /H ₂ 0) aqueous solution (70 mL) was added and refluxed for 6 hours. After cooling the reaction solution to room temperature, the organic layer was extracted. The reaction solution was concentrated and recrystallized with ethanol to obtain compound 3 (8.9 g, yield 92%).

MS: [M+H] ⁺ =348

Compound 3 (8.2 g, 23.6 mmol) was dissolved in DMF (200 mL), N-bromo succinimide (4.15 g, 23.6 mmol) was added, followed by stirring at room temperature for 5 hours. Distilled water was added to the reaction solution, and then the organic layer was extracted. The reaction solution was concentrated and recrystallized with ethanol to obtain compound 4 (8.25 g, yield 82%).

MS: [M+H] ⁺ =427

Methyltriphenylphosphonium bromide (13.41 g, 37.532 mmol) and potassium t-butoxide (4.21 g, 37.532 mmol) were added to anhydrous THF (300 mL) and stirred first. Thereafter, compound 4 (8 g, 18.766 mmol) dissolved in anhydrous THF (60 mL) was slowly added dropwise and reacted for 5 hours. After the reaction was terminated with an aqueous sodium carbonate solution, the organic layer was extracted with methylene chloride and water, and residual moisture was removed using MgSO ₄ . The reaction solution was concentrated and then subjected to column chromatography with methylene chloride and hexane to obtain compound 5 (7.8g, 98%).

MS: [M+H] ⁺ =425

Compound 5 (2 g, 4.713 mmol) and (4-chlorophenyl) boronic acid (1.1 g, 7.069 mmol) were dissolved in anhydrous THF (20 mL), and then Pd(PPh ₃ ) ₄ (0.32 g, 0.28 mmol) and 2M potassium carbonate (K ₂ CO ₃ /H ₂ 0) aqueous solution (15 mL) was added and refluxed for 6 hours. After cooling the reaction solution to room temperature, the organic layer was extracted. The reaction solution was concentrated and recrystallized with ethanol to obtain compound 6 (2 g, yield 93%).

MS: [M+H] ⁺ =457

[Production Example 1]

Preparation Example 1-1: Preparation of Compound A1

Compound 5 (3.65 g, 8.615 mmol), (4-(diphenylamino) phenyl) boronic acid (2.99 g, 10.338 mmol), Pd(PPh ₃ ) ₄ (498 mg, 0.431 mmol), and K ₂ CO ₃ ( 3.57 g, 25.845 mmol) was dissolved in THF (43 mL) and distilled water (15 mL) and stirred at 70° C. for 15 hours. The organic layer was extracted using ethyl acetate and water. After dehydration using MgSO ₄ , the solvent was removed under reduced pressure. The obtained material was subjected to column chromatography with ethyl acetate and hexane to prepare compound A1.

MS: [M+H] ⁺ =589

Preparation Example 1-2: Preparation of Compound A2

Compound A2 was prepared in the same manner as in the preparation of Compound A1, except that (4-(dibiphenyl-4-ylamino)phenyl)boronic acid was used instead of (4-(diphenylamino)phenyl)boronic acid. .

MS: [M+H] ⁺ =741

Preparation Example 1-3: Preparation of Compound A3

Except that (4-(biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)phenyl)boronic acid was used instead of (4-(diphenylamino)phenyl)boronic acid. Is, compound A3 was prepared in the same manner as in the production method of compound A1.

MS: [M+H] ⁺ =782

Preparation Example 1-4: Preparation of Compound A4

Compound 5 (3.65 g, 8.615 mmol), diphenylamine (1.74 g, 10.338 mmol), Pd(t-Bu ₃ P) ₂ (220 mg, 0.431 mmol), and sodium t-butoxide (2.48 g, 25.845 mmol) ) Was dissolved in toluene (26 mL) and stirred at 100° C. for 15 hours. The organic layer was extracted using ethyl acetate and water. After dehydration using MgSO ₄ , the solvent was removed under reduced pressure. The obtained material was subjected to column chromatography with ethyl acetate and hexane to prepare compound A4.

MS: [M+H] ⁺ =513

Preparation Example 1-5: Preparation of Compound A5

Compound A5 was prepared in the same manner as in the preparation method of Compound A4, except that dibiphenyl-4-ylamine was used instead of diphenylamine.

MS: [M+H] ⁺ =665

Preparation Example 1-6: Preparation of Compound A6

Compound A6 was prepared in the same manner as in the preparation method of Compound A4, except that N-(biphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine was used instead of diphenylamine. .

MS: [M+H] ⁺ =665

Preparation Example 1-7: Preparation of Compound A7

Compound A7 was prepared in the same manner as in the preparation method of Compound A1, except that Compound 6 was used instead of Compound 5.

MS: [M+H] ⁺ =665

Preparation Example 1-8: Preparation of Compound A8

Preparation method of compound A1, except that compound 6 was used instead of compound 5, and (4-(dibiphenyl-4-ylamino)phenyl) boronic acid was used instead of (4-(diphenylamino)phenyl)boronic acid Compound A8 was prepared in the same manner as described above.

MS: [M+H] ⁺ =818

Preparation Example 1-9: Preparation of Compound A9

Compound 6 was used instead of compound 5, and 4-(biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)phenyl was used instead of (4-(diphenylamino)phenyl)boronic acid. Compound A9 was prepared in the same manner as in the preparation method of Compound A1, except that boronic acid was used.

MS: [M+H] ⁺ =858

[Production Example 2]

Preparation Example 2-1: Preparation of Compound B2

(4-formylphenyl)boronic acid (4.91 g, 32.778 mmol) and 3-bromobicyclo[4.2.0]octa-1(6),2,4-triene (5 g, 27.315 mmol) were added to Pd(PPh) ₃ ) ₄ (1.58 g, 1.366 mmol), and K ₂ CO ₃ (11.32 g, 81.945 mmol) were dissolved in THF (200 mL) and distilled water (100 mL) and stirred at 70° C. for 15 hours. The organic layer was extracted using ethyl acetate and water. After dehydration using MgSO ₄ , the solvent was removed under reduced pressure. The obtained material was subjected to column chromatography with ethyl acetate and hexane to prepare compound 7.

MS: [M+H] ⁺ =209

Methyl triphenylphosphonium bromide (13.41 g, 37.532 mmol) and potassium t-butoxide (4.21 g, 37.532 mmol) were added to anhydrous THF (30 mL) and stirred. Then, compound 7 (3.90 g, 18.766 mmol) dissolved in anhydrous THF (10 mL) was slowly added dropwise and reacted for 4 hours. After the reaction was terminated with an aqueous sodium carbonate solution, the organic layer was extracted using methylene chloride and water, and the residual moisture was removed using MgSO ₄ . The reaction solution was concentrated and then subjected to column chromatography with methylene chloride and hexane to prepare compound B2 (3.2 g, yield 84%).

MS: [M+H] ⁺ =207

[Production Example 3]

Preparation Example 3-1: Preparation of Compound D1

After dissolving 2-bromo-9H-fluorene-9-one (5 g) in THF (50 mL), phenylmagnesium bromide (11 mL, 3 M solution in ether) was added at 0° C. and stirred for 30 minutes. After the reaction was terminated with an aqueous ammonium chloride solution, the mixture was extracted into an organic layer using ethyl acetate and water. The residual water of the organic layer was removed with MgSO ₄ , filtered, and the filtrate was filtered using a vacuum concentrator to remove the solvent and purified by MPLC to obtain compound 14 (5.4 g).

Compound 14 (5.4 g) was dissolved in methylene chloride (40 mL), TESH (3.84 mL) and TFA (1.9 mL) were slowly added dropwise, followed by stirring at room temperature for 16 hours. This was extracted into an organic layer using methylene chloride and water, and the residual water was removed with MgSO ₄ and the solvent was removed by a vacuum concentrator. The obtained solid was purified using MPLC to obtain compound 15 (4.8 g).

Compound 15 (1 g) was dissolved in toluene (10 mL), and TBAB (0.1 g), NaOH (0.4 g), and water (2 mL) were added and stirred first. After 6-bromohexene (0.6 mL) was added and reacted overnight at 120°C, the organic layer was extracted using ethyl acetate and water. After removing water remaining in the organic layer with MgSO ₄ , the solvent was removed by a vacuum concentrator and purified by MPLC to obtain compound 16 (0.7 g).

Compound 16 (1.7 g, 4.22 mmol), 4-vinylbenzeneboronic acid (750 mg, 5.06 mmol), Pd(PPh ₃ ) ₄ (243 mg, 0.21 mmol), and K ₂ CO ₃ (1.75 g, 12.65 mmol) Was placed in a round bottom flask and replaced with nitrogen. After adding THF (17 mL) and H ₂ O (4.2 mL), the mixture was stirred at 90°C for 4 hours. The organic layer was extracted using ethyl acetate and water. Water remaining in the organic layer was removed with MgSO ₄ and filtered. The filtrate was dried in vacuo and purified by MPLC to obtain compound D1 (950 mg).

MS: [M+H] ⁺ = 427

Preparation Example 3-2: Preparation of Compound D2

Compound D2 was prepared in the same manner as in the preparation method of compound D1, except that 8-bromooctene was used instead of 6-bromohexene.

MS: [M+H] ⁺ =455

[Example]

Example 1: Preparation of Copolymer C1

Compound A1 (500 mg), compound B2 (22 mg), compound D1 (45 mg), and AIBN (1.2 mg) prepared above were added to toluene and reacted at 100° C. for 14 hours under nitrogen substitution. Precipitated in ethyl acetate to prepare a synthesized polymer C1. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:37100, Mw:78600

Example 2: Preparation of Copolymer C2

Preparation of Copolymer C1, except that Compound A3 was used instead of Compound A1 and 3-vinyl-bicyclo[4.2.0]octa-1(6),2,4-triene was used instead of Compound B2. Copolymer C2 was prepared in the same way. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:45700, Mw:97400

Example 3: Preparation of Copolymer C3

Except that Compound A6 was used instead of Compound A1, 3-vinyl-bicyclo[4.2.0]octa-1(6),2,4-triene was used instead of Compound B2, and Compound D2 was used instead of Compound D1. Then, copolymer C3 was prepared in the same manner as in the preparation of copolymer C1. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:39200, Mw:62400

Example 4: Preparation of Copolymer C4

Copolymer C4 was prepared in the same manner as in Copolymer C1, except that Compound A9 was used instead of Compound A1. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:35900, Mw:73100

Example 5: Preparation of Copolymer C5

Compound A1 (500 mg), compound B2 (44 mg), compound D1 (90 mg), and AIBN (1.2 mg) prepared above were added to toluene and reacted at 100° C. for 14 hours under nitrogen substitution. Precipitated in ethyl acetate to prepare a synthesized copolymer C5. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:45030, Mw:92770

Example 6: Preparation of Copolymer C6

Preparation of Copolymer C1, except that Compound A3 was used instead of Compound A1 and 3-vinyl-bicyclo[4.2.0]octa-1(6),2,4-triene was used instead of Compound B2. Copolymer C6 was prepared in the same way. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:32560, Mw:74470

Comparative Example: Preparation of Copolymer F

(1) Preparation of compound 11

Compound 9 (4-(9H-carbazol-9-yl)benzaldehyde, 10 g, 26.856 mmol) and NBS (N-bromosuccinimide, 6.62 g, 37.225 mmol) were added to DMF (184 mL) and 4 After stirring for a period of time, the organic layer was extracted using ethyl acetate and water. After dehydration using MgSO ₄ , the solvent was removed under reduced pressure. The obtained material was subjected to column chromatography with ethyl acetate and hexane to obtain compound 10 (12.5 g, yield: 97%).

MS: [M+H] ⁺ =351

Methyltriphenylphosphonium bromide (15.3 g, 42.830 mmol) and potassium t-butoxide (6.4 g, 57.106 mmol) were added to THF (70 mL) and stirred, followed by compound 10 (10 g, 28.553 mmol) prepared above. It was further put and stirred for 4 hours. After removing the residual base using a saturated sodium bicarbonate aqueous solution, the organic layer was extracted using ethyl acetate and water. After dehydration using MgSO ₄ , the solvent was removed under reduced pressure. The obtained material was subjected to column chromatography with ethyl acetate and hexane to obtain compound 11 (9.5 g, yield: 96%).

MS: [M+H] ⁺ =349

(2) Preparation of compound 12

Compound 11 (3 g, 8.615 mmol) prepared above, (4-(diphenylamino) phenyl) boronic acid (2.99 g, 10.338 mmol), Pd(PPh ₃ ) ₄ (498 mg, 0.431 mmol), and K ₂ CO ₃ (3.57 g, 25.845 mmol) was dissolved in THF (43 mL) and distilled water (15 mL), and stirred at 70° C. for 15 hours. The organic layer was extracted using ethyl acetate and water. After dehydration using MgSO ₄ , the solvent was removed under reduced pressure. The obtained material was subjected to column chromatography with ethyl acetate and hexane to prepare compound 12.

MS: [M+H] ⁺ =513

(3) Preparation of copolymer F

It was prepared in the same manner as the method for preparing copolymer C1, but using compound 12 and compound B2 as starting materials, and adjusting the equivalent weight to prepare copolymer F. The number average molecular weight and weight average molecular weight of the prepared polymer were measured by GPC using a PC standard using an Agilent 1200 series.

Mn:37800, Mw:77900

[Experimental Example]

Experimental Example 1-1

A glass substrate coated with a thin film of 1,500Å of ITO (indium tin oxide) was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water was finished, ultrasonic cleaning was performed with a solvent of isopropyl and acetone, followed by drying, the substrate was washed for 5 minutes, and the substrate was transported to a glove box.

On the ITO transparent electrode, 2 wt% toluene ink of the previously prepared copolymer C1 and the following compound M (8:2 by weight) was spin-coated (4000 rpm) and heat-treated (cured) at 200° C. for 30 minutes to a thickness of 40 nm. A hole injection layer was formed. After transferring to a vacuum evaporator, the following Compound G was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 20 nm. The following compound H and the following compound I were vacuum-deposited on the hole transport layer at a weight ratio of 92:8 to a thickness of 20 nm to form a light emitting layer. The following compound J was vacuum-deposited to a thickness of 35 nm on the emission layer to form an electron injection and transport layer. A cathode was formed by sequentially depositing LiF to a thickness of 1 nm and aluminum to a thickness of 100 nm on the electron injection and transport layer.

In the above process, the deposition rate of organic matter was maintained at 0.4 ~ 0.7 Å/sec, LiF was 0.3 Å/sec, and aluminum was maintained at a deposition rate of 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ 5 ×10 ^-8 torr was maintained.

Experimental Examples 1-2 to 1-4

An organic light emitting device was manufactured in the same manner as in Experimental Example 1-1, except that the copolymer shown in Table 1 was used instead of the copolymer C1.

Comparative Experimental Example 1

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that the copolymer F was used instead of the copolymer C1.

Table 1 shows the results of measuring the driving voltage, external quantum efficiency (EQE), luminance, and lifetime of the organic light emitting device prepared in the above Experimental Examples and Comparative Experimental Examples at a current density of 10 mA/cm ² . Done. The external quantum efficiency was calculated as (number of emitted photons)/(number of injected charge carriers). T80 refers to the time it takes for the luminance to decrease from the initial luminance (500 nit) to 80%.

Hole injection layer Driving voltage (V) J(mA/cm ² ) EQE(%) Life (hr)
(T80@500 nit) Experimental Example 1-1 Copolymer C1 4.38 10 5.8 140 Experimental Example 1-2 Copolymer C2 4.24 10 6.1 159 Experimental Example 1-3 Copolymer C3 4.31 10 6.8 154 Experimental Example 1-4 Copolymer C4 4.83 10 5.3 172 Comparative Experimental Example 1 Copolymer F 5.13 10 4.4 105

As shown in Table 1, it was confirmed that the copolymer according to the present invention comprises Chemical Formula 1 and Chemical Formula 3, and thus, the efficiency and lifespan are improved compared to the copolymer that does not. In addition, the copolymer according to the present invention has excellent solubility in an organic solvent, and it is easy to prepare a coating composition. As a result of Table 1, it was confirmed that a uniform coating layer could be formed by using the coating composition, and the stability of the film was also excellent, so that more excellent performance was exhibited in the organic light emitting device.

Experimental Example 2-1

A glass substrate on which a thin film of ITO (indium tin oxide) was deposited with a thickness of 1500Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol and acetone for 30 minutes each, followed by drying, and the substrate was transported to a glove box.

On the thus prepared ITO transparent electrode, the following compound A'and the following compound M were mixed at a weight ratio of 8:2, and a solution dissolved in cyclohexanone was spin-coated to form a film with a thickness of 400Å. This was heated at 220° C. for 30 minutes in a nitrogen atmosphere to form a hole injection layer. The previously prepared copolymer C1 was dissolved in toluene, spin-coated on the hole injection layer to form a film at 200Å, and heated at 190° C. for 1 hour in a nitrogen atmosphere to form a hole transport layer. On the hole transport layer, a solution obtained by dissolving the following compound H and the following compound I in cyclohexanone at a weight ratio of 92:8 was spin-coated to form a film at 200 Å and heated at 120° C. for 1 hour in a nitrogen atmosphere to form a light emitting layer. The following compound J was vacuum-deposited on the light emitting layer to a thickness of 35 nm to form an electron injection and transport layer. A cathode was formed by sequentially depositing LiF to a thickness of 1 nm and aluminum to a thickness of 100 nm on the electron injection and transport layer.

In the above process, the deposition rate of organic materials was maintained at 0.4 ~ 0.7 Å/sec, LiF was 0.3 Å/sec, and aluminum was maintained at a deposition rate of 2 Å /sec, and the vacuum degree during deposition was 2×10 ^-7 ~ 5 ×10 ^-8 torr was maintained.

Experimental Examples 2-2 to 2-6

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that the copolymer described in Table 2 was used instead of the copolymer C1.

Comparative Experiment 2

An organic light emitting device was manufactured in the same manner as in Experimental Example 2-1, except that the copolymer F was used instead of the copolymer C1.

Table 2 shows the results of measuring the driving voltage, external quantum efficiency (EQE), luminance, and lifetime of the organic light-emitting device prepared in the Experimental Examples and Comparative Experimental Examples at a current density of 10 mA/cm ² . Done. The external quantum efficiency was calculated as (number of emitted photons)/(number of injected charge carriers). T80 refers to the time it takes for the luminance to decrease from the initial luminance (500 nit) to 80%.

Hole transport layer Driving voltage (V) J(mA/cm ² ) EQE(%) Life (hr)
(T80@500 nit) Experimental Example 2-1 Copolymer C1 4.45 10 5.7 135 Experimental Example 2-2 Copolymer C2 4.33 10 5.9 99 Experimental Example 2-3 Copolymer C3 4.51 10 6.4 105 Experimental Example 2-4 Copolymer C4 4.31 10 5.3 115 Experimental Example 2-5 Copolymer C5 4.49 10 5.6 87 Experimental Example 2-6 Copolymer C6 4.95 10 5.3 91 Comparative Experiment 2 Copolymer F 6.13 10 3.9 52

As shown in Table 2, it was confirmed that the copolymer according to the present invention contained Chemical Formulas 1 and 3, and thus, the efficiency and lifespan were improved compared to the copolymers that did not. In addition, the copolymer according to the present invention has excellent solubility in an organic solvent, and it is easy to prepare a coating composition. As a result of Table 2, it was confirmed that a uniform coating layer can be formed by using the coating composition, and the stability of the film is also excellent, so that the organic light emitting device exhibits better performance.

1: substrate 2: anode
3: hole transport layer 4: light emitting layer
5: cathode 6: hole injection layer
7: electron transport layer 8: electron injection layer

Claims (15)

A polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3):
[Formula 1]

In Formula 1,
R ₁ to R ₃ are each independently hydrogen or C _1-10 alkyl,
L ₁ is substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,
L ₂ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,
Ar ₁ is substituted or unsubstituted C _6-60 aryl, or C _2-60 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
Ar ₂ and Ar ₃ are each independently selected from the group consisting of substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O and S C _2-60 heteroaryl including any one or more,
[Formula 2]

In Chemical Formula 2,
R ₄ to R ₆ are each independently hydrogen or C _1-10 alkyl,
L ₃ is a single bond; Substituted or unsubstituted C _6-60 arylene; (Substituted or unsubstituted C _6-60 arylene)-O-; (Substituted or unsubstituted C _6-60 arylene)-O-(substituted or unsubstituted C _1-60 alkylene); Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,
[Formula 3]

In Chemical Formula 3,
R ₇ to R ₉ are each independently hydrogen or C _1-10 alkyl,
L ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more selected from the group consisting of N, O and S,
Ar ₄ is substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O and S containing any one or more selected from the group consisting of C _2-60 heteroaryl,
Ar ₅ is hydrogen or substituted or unsubstituted C _6-60 aryl,
n is an integer from 0 to 5.
The method of claim 1,
x:y:z is 0.5~0.9: 0.05~0.45: 0.05~0.45,
Polymer.
The method of claim 1,
L ₁ is phenylene, or biphenylylene,
Polymer.
The method of claim 1,
L ₂ is a single bond, phenylene, biphenylylene, or terphenylylene,
Polymer.
The method of claim 1,
Ar ₁ is phenyl, biphenylyl, dimethylfluorenyl, or diphenylfluorenyl, and Ar ₁ is unsubstituted or methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, methoxy , Substituted with ethoxy, propoxy, butoxy, isobutoxy, or neobutoxy,
Polymer.
The method of claim 1,
Ar ₂ and Ar ₃ are each independently phenyl, biphenylyl, dimethylfluorenyl, or diphenylfluorenyl,
Polymer.
The method of claim 1,
Formula 1 is any one selected from the group consisting of repeating units represented by the following,
Polymer:

The method of claim 1,
L ₃ is a single bond, phenylene, -(phenylene)-O-, -(phenylene)-O-(butane-1,4-diyl), or biphenylylene,
Polymer.
The method of claim 1,
Formula 2 is any one selected from the group consisting of repeating units represented by the following,
Polymer:

The method of claim 1,
L ₄ is a single bond, phenylene, or biphenylylene,
Polymer.
The method of claim 1,
Ar ₄ is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, phenyl substituted with one or two C _1-4 alkyl, or biphenylyl,
Polymer.
The method of claim 1,
Ar ₅ is hydrogen, phenyl, biphenylyl, terphenylyl, or quarterphenylyl,
Polymer.
The method of claim 1,
Formula 3 is any one selected from the group consisting of repeating units represented by the following,
Polymer:

The method of claim 1,
The weight average molecular weight of the polymer is 5,000 to 1,000,000,
Polymer.
anode; A cathode provided to face the anode; A light-emitting layer provided between the anode and the cathode; And a hole transport layer provided between the anode and the light emitting layer, wherein the hole transport layer comprises a polymer according to any one of claims 1 to 14.

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